TW200537994A - Metal-coated resin molded article and production method thereof - Google Patents

Abstract

A metal-coated resin molded article is provided, which has improved adhesion between a metal layer and a substrate of a resin composition as well as excellent malleability, heat resistance, electronic and mechanical properties. The resin composition comprises a liquid-crystalline polyester and an epoxy-group containing ethylene copolymer. The molecule containing the epoxy-group of the ethylene copolymer contains 50 to 99.9 wt% of an ethylene unit and 0.1 to 30 wt% of at least one of an unsaturated carboxylic acid glycidyl ester unit and an unsaturated glycidyl ether unit. A content of the epoxy-group of the ethylene copolymer is in a range of 0.1 to 25 parts by weight with respect to 100 parts by weight of the liquid-crystalline polyester.

Description

200537994 IX. Description of the invention: [Technical field to which the invention belongs] The present invention provides a metal-coated resin casting and a dream making method thereof. Lu Zhi uses a liquid crystal polyester as a substrate, which can be applied to thunder toilets. [Previous Technology] ~, private fruit. In the past, liquid crystal polyester has been widely used as a raw material for electronic fish machinery. Liquid crystal polyester has excellent properties in the following properties, such as electrical properties, heat resistance, chemical resistance, and flame resistance. And mechanical #. As an example, the circuit = white = and is obtained by forming a metal film on a resin substrate, which contains a liquid crystal polyester, which has been experimentally proven to have good plasticity, stable elastic coefficient, and acid, and It is difficult to interconnect the castings_also expected—a material :. However, in the above, it is not easy to obtain a metal film with strong adhesion because there is no chemical bond between the substrate and the metal film. Especially after a negative thermal load, the adhesion of the metal film will decrease. The use of liquid crystal poly circuit boards, such as those obtained by Japanese patent circuit boards, is made by casting a resin substrate or a resin substrate. When the vacuum chamber 2 = handles to obtain a surface temperature of more than 6CTC, after the break, ^ & 'make the resin-based surface of the resin substrate deposited on the resin substrate' or true conversion method, in addition to Japanese Patent 7 No. 24328, part manufacturing method. The fine circuit is formed by casting a person y, a resin composite H 7 night crystal polyester for casting a thin circuit, and an inorganic filler engraving treatment to make the resin base broader: a substrate. A money mirror, or a shaft plating, and ion electricity are used. According to the roughened surface = nano layer, a metal film is deposited. Increasing the contact area is called the quasi-effect and the improvement of the -force energy between the resin substrate and the metal film. _, Here is expected-a question ^ 200537994 due to increased surface roughening. The reduction in this matter. That is, the formation of fine circuits becomes difficult. In the example, the decrease in the accuracy of the circuit will lead to the output. [Abstract] The main purpose of the present invention is to improve the crystal polyester as the main component between a metal-coated resin casting and the substrate. Provide-and its manufacturing method, the adhesion of the resin casting to the metal film, and the resin turning member is made of a liquid resin composition.

The metal-coated resin component of the present invention includes a substrate made of a resin composition and a metal film formed on the substrate. The domain lipid composition includes a liquid crystal fluorene and a ring containing an ethylene copolymer. Oxygen. The molecule containing the epoxy group of the ethylene copolymer contains-5 to 99.9 weight percent of ethylene, and at least one G.1 dragon weight percentage of unsaturated Wei shrinkage material units and-saturated. 1 至 25 重量 ％。 Age Ganlai unit, about 100% by weight of the liquid crystal poly § intent, the content of the epoxy group containing ethylene copolymer ranges from 0.1 to 25 weight percent. According to the present invention, the adhesion of the metal film can be improved by using the above-mentioned specific resin composition without the need for surface-peaking treatment of the substrate. Therefore, it promotes the supply of a casting circuit board with good circuit adhesion such as a metal-coated resin casting. A further object of the present invention is to provide a method for manufacturing a metal-coated resin part, which is characterized by the following steps: casting-a resin is synthesized to obtain a substrate; and forming a metal film on the surface of the substrate. The resin composition includes a liquid crystal polyacetate and a polymer containing an ethylene copolymer. The molecule containing the epoxy group of the ethylene copolymer contains a 50 to 99.9 weight percent ethylene unit and at least one 6 200537994 unsaturated glycidol unit and one vinegar, containing the weight percentage of ethyl material. Percentage of liquid crystal poly. The domain-containing mesh of the base is 0.1 to 25% by weight; gold is included; the formation of gold = the film is formed by a physical vapor phase. More than

With the drawings, it is believed that the present invention :: 二 = 发, incomprehensible and specific understanding, but the attached Wei Er is obtained from this-not for the purpose of limiting the present invention for the purpose of explanation,-[贯 施 / Type 7] The main focus of the resin composition is a coating composition, "Liquid," said. It is good to form one for an aromatic backbone; for the poor melting phase, for example, an anti-Yong + 彳 /, pre-j reaction products are obtained by at least one Fangri & Di-S-exchange and aromatic condensation reaction with aromatic Gu Jilai, and the preparation of a fluorinated compound is by hydration of at least one aromatic monohydric alcohol and an aromatic tribasic acid with fatty acid anhydride Of a phenol group. For example, when it is an aromatic diol, 4,4, _dihydroxybiphenyl, hydroquinone, resorcinol, fluorenylhydroquinone, chlorohydroquinone, and acetaminophen Diphenol, nitrogen hydroquinone, 1,4-dihydroxynaphthalene, diaphthylnaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, 2 · bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5, xylyl) propane ', 2,2_bis (4_ 赵 基 _3,5_dichloro Phenyl) propane, 2,2_bis (tolyl), tolyl, propylene, 2,2_bis (4-Cyridyl-3-chlorobenzyl), Cryptoin, bis (fluorenylphenyl) methyl Institute, 7 200537994 bis (4-hydroxy-3,5-xylyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3- 曱 phenyl) 曱Alkane, bis (4-hydroxy-3-chlorophenyl) pinene, U-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ketone , Bis (4-hydroxy-3,5-diphenylphenyl) ketone, bis (4-hydroxydichlorophenyl) ketone, bis (4-hydroxyphenyl) fluorene. When it is an aromatic diol, one of these compounds is used in combination with two or more fluorenes. In particular, the use of 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,2- Bis (4-hydroxyphenyl) propane or bis (4-hydroxyphenyl) sulfone. On the other hand, when it is an aromatic hydroxycarboxylic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy- 4-naphthol, 4-hydroxy-4'-carboxydiphenyl ether, 2,6-dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2,6-difluoro-p Hydroxybenzoic acid or 4-hydroxy-4, diphenylcarboxylic acid. In the case of an aromatic hydroxycarboxylic acid, one of these compounds may be combined with two or more to be amidines. In particular, it is preferable to use p-hydroxybenzoic acid or 2-hydroxy-6-naphthalic acid from the viewpoint of the prior art. In addition, for example, when it is an aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-dibenzene may be used. Dicarboxylic acid, ethyl terephthalate, methyl isophthalate, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenyl Ketone-4,4'-dicarboxylic acid or 2,2'-diphenylpropane-4,4'-dicarboxylic acid. When it is an aromatic dicarboxylic acid, one of these compounds is used in combination with two or more. In particular, it is preferable to use terephthalic acid, isophthalic acid, or 2,6-naphthalenedicarboxylic acid from the viewpoint of the prior art. For example, when it is a fatty acid anhydride, acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, chlorine 8 200537994 acetic anhydride, dichloroacetic anhydride, trichloroacetic acid may be used. -, San Mo is called Qi Yi, Di Qi E Ding: Diacid V Diacid Anhydride, or Moproic Anhydride, used. Especially from the cost and tolerance theory, ", and called anhydride, butyric anhydride or isobutyric anhydride, especially acetic acid. There is a good power between the substrate and the metal layer of the attached casting, 仏 is the in-place compound The reaction in the presence is shown in chemical formula (i). 佚 / 、 来 细 σ

Ri τντ

(In the chemical formula (1), R to R represent a fluorenyl group having a number of! To 4; two, a cyanoalkyl group having a carbon atom of "-1g 'with a carbon number of 2 to 4 and a carbon atom; The number is 4 to 4, and the number of carbons, aminos, and carbon atoms is ^ and mesityl.) Minus base, fluorenyl, and phenylpropanyl = If the side = compound is represented by the chemical formula ⑴, it may make 丄, a Imidazole, 2-amidoimidazole, 4-methylimidazole, r ^, azole main 4-methylimidazole, 1-ethylimidazole, 2-ethylimidazoleethylimidazole, 1,2--methyl Imidazole, dimethyl dimethyl imidazole, 2 4-dimethyl-2-ethylimidazolium, μ methyl benzyl ethyl salivary, [ethyl aspartate V, wow, 1-ethyl-2- Ethyl imidazolium, μ ethyl j phenyl sigma, 2 ethyl acetomethyl ^ 9 200537994 imidazole, 2-phenylimidazole, 2-undecylimidazole, 2 heptylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, μcyanoethylmethylimidazole, cyanoethyl-2-phenylimidazole, 4-cyanoethyl-2-ethyl -Methylimidazole or 1-aminoethylmethylimidazole. The preferred imidazole compound R1 is an alkyl group having a number of carbon atoms and 4 & R4 is a hydrogen atom. In addition, it is preferable to use 1-methylimidazolium or 2-methylimidazolium from an existing viewpoint. In the above-mentioned transesterification and polycondensation reaction, the fluorinated compound and fragrant The number of dicarboxylic acids and / or aromatic hydroxycarboxylic acids is measured, and the number of aromatic groups and / or aromatic μ-based fluorenes is used to prepare intoxicated compounds. Equivalent number of hydroxyl groups is 08 In the range of 12, Guangxi corresponds to the aromatic two-base and / or aromatic base test. Sub: When the temperature rise ratio is 0.1 ~ 50t: / min, the transesterification reaction is performed in 130 ~ 40CTC. It is better; when the rate of increase of the degree of month is / mm, it is better to carry out the transesterification reaction at a temperature of 150 ~ 35 ° c> c. When it is an acylated compound, it may make two products 'Is obtained in the -domain response container, shredded fat-free, two-denier-compounds have __chemical bridging group = 疋: Γ Lai Jingji equivalent number is 1 ° 5 to 1.1 and / or aromatic' hydroxyl : In terms of the number of base shellfish, when the number of fatty acid anhydrides is less than the polycondensation time of liquid aSxKg, it will cause the sublimation of the raw materials, and 3 Nakaira Hikaru dreams because the H-fat is easy to block. In this example, the reaction system is at 1.2, and the number of bases is equal to ^. The number of fatty anhydrides is randomized .: Two have problems In addition, the conditions are 30 minutes to 20 hours and the temperature is 10 200537994 130C to 180C, and the better condition is 1 hour to 5 hours and the temperature is 140 ° C to 160 ° C. An equilibrium shift is used to promote the vinegar exchange reaction between fatty acid esters and carboxylic acids. Preferably, the by-product fatty acids and unreacted lipoumic anhydride are evaporated and removed from the reaction system. In addition, when a part of the evaporated fat 酉 夂 flows back to the reaction valley, the raw material components and the countercurrent fatty acid which are evaporated or sublimated by condensation or reversible sublimation can flow back to the reaction container.

In the paternity polycondensation reaction, the amount of the chemical formula (1) of an additive imidazole compound is 0.005 to 1 weight percent, which is about 100 weight percent of the entire aromatic di-acid, diol, and hydroxycarboxylic acid. Used to synthesize liquid crystal polyacetate. From the viewpoint of the color tone and productivity of the crystal polysilicon, a better additive is a compound: the number is 0.05 to 0.5% by weight. When the amount of the additive is less than 0.5%, the compound will not sufficiently accelerate the transesterification and polycondensation reaction. Once the amount of the additive is greater than 1 weight percent, the oxazole compound will 2. The reaction system. At the time of the vinegar exchange, the presence of the compound and the timing of the reaction system and the compound are not affected. Therefore, the imidazole compound should be added immediately during the transesterification or the reaction process. The catalyst is used to accelerate the transesterification and polycondensation reaction. Oxalic acid contains a complex compound such as a complex oxide, a tin compound such as a titanium oxide such as titanium dioxide, a diaryl tin oxide, and a titanium compound such as trigas-alkylated titanium, Alkoxy titanium silicate, antimony compound calcium, samarium; 铉,:, · acid metal salts such as sodium acetate, potassium acetate, acetic acid, zinc zinc, and iron acetate, acetonide; ^ amino aminated characters, Λ tolerance For example, boron trifluoride, aluminum chloride, and other compounds such as hydrochloric acid and sulfuric acid should be prepared by the condensation of esters and polycondensation. Each of them is aromatic by optical difference. Backbone formation-melting phase. In Hei 11 200537994 On the one hand, the liquid crystal polyester has financial heat and financial impact. The preferred liquid crystal polyester contains at least 30 mol% of repeating units, which is represented by the chemical formula (2). In addition, the molecular weight of the liquid crystal polystyrene is not limited. The average molecular weight of the ester is 10,000 to 50,000.

In addition, the repeating units in the liquid crystal polyester are selected from the following compounds (a) to (f) based on the aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and aromatic diol. (a) Compounds based on p-hydroxybenzoic acid, based on terephthalic acid or mixed terephthalic acid and isophthalic acid, and based on 4,4'-dihydroxydiphenyl. (b) A compound obtained by substituting a structural unit based on a structural unit of hydroquinone for a part or all of 4,4'-dihydroxydiphenyl in compound (a). (c) A compound obtained by substituting part or all of the 4,4'-dihydroxydiphenyl structural unit in the compound (a) for the structural unit of resorcinol. (d) A compound obtained by substituting a structural unit based on 2,6-dihydroxynaphthalene for a part or all of 4,4'-dihydroxydiphenyl in compound (a). (e) Substitute the 4,4'-dihydroxydiphenyl group in the compound (a) according to the structural unit of the mixed 2,6-dihydroxynaphthalene and 2,2-bis (4-hydroxyphenyl) propane. Part or all of the structural unit, the compound 12 200537994 obtained. (f) Compound obtained by substituting a structural unit based on 2-hydroxy-6-nelic acid for the compound (a) based on a part or all of p-hydroxybenzoic acid.

Then, the "bad milk base" is described as including an ethylene fine copolymer, which is the main component of the resin composition constituting the metal-coated resin casting of the present invention. In the present invention, the epoxy group includes an ethylene copolymer, and the ethylene copolymer includes 50 to 99.9 weight percent of ethylene units and 0.1 to 30 weight percent of at least one unsaturated slow acid glycidyl ester unit and unsaturated glycidyl bond unit. . In addition to these units, the epoxy group contains an ethylene copolymer if necessary, and the ethylene copolymer contains an ethylene unsaturated ester unit. In this case, the number of ethylene unsaturated ester units is preferably 50% by weight or less.

To obtain a good heat-resistant and tough resin substrate and further improve the adhesion of the metal layer, the preferred epoxy group in the present invention comprises an ethylene copolymer, which comprises 80 to 95 weight percent of ethylene units and 5 to 15 weight percent of at least one unsaturated carboxylic acid glycidyl ester unit and unsaturated glycidyl ether unit. For example, the unsaturated glycidyl ester units and unsaturated glycidyl ether units of these compounds are shown in the following chemical formulas (3) and (4),

R —C —〇—CH2—CH—CH2 〇

Wherein in the chemical formula (3), R is a hydrocarbon compound, the number of carbon atoms of which is 2 to 13, and an ethyl hydrazone unsaturated bond. R—X — CH2 —CH—CH2 〇 13 ... (4) 200537994 wherein R in the chemical formula (4) is a hydrocarbon compound, and the number of carbon atoms thereof is 2 to 1. And an ethylene unsaturated bond, and X is the following chemical formula.

In particular it may use glycidyl acrylate, glycidyl methacrylate, glycidyl ester of itaconic acid, allyl glycidyl ether, 2-methacryl glycidyl ether, or styrene-P-glycidyl ether , Or similar. When the epoxy group contains an ethylene copolymer, a ternary or more copolymer is used, which in addition to ethylene contains an ethylene unsaturated ester and an unsaturated carboxylic acid glycidyl ester and / or an unsaturated glycidyl ester. Glyceryl ether. In the case of hexene unsaturated ester compounds, for example, it is possible to use a carboxylic acid vinyl ester such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl propionate, methyl methacrylate, fluorene Ethyl acrylate and fluorenyl butyl acrylate or α, β-unsaturated carboxylic acid alkyl ester. It is particularly preferred to use ethylene acetate, ethyl acrylate or ethyl acrylate. Epoxy groups containing ethylene copolymers are prepared by copolymerization of a compound that is an ethylene unit, an unsaturated carboxylic acid 'water glycerol target unit, or an unsaturated fine water glycerol test unit and if one is required The compound is an ethylene unsaturated ester unit at a pressure of 500 to 400 atm and a temperature of 100 to 300 ° C in the presence of a free radical generator. If necessary, the copolymerization reaction can be performed in the presence of a suitable solvent or a chain conversion reagent. In particular, for example, an epoxy group containing an ethylene copolymer, which can be used. Copolymers include ethylene monomers and glycidyl ether units of methacrylic acid. Copolymers include ethylene units, glycidyl methacrylate. Ether unit 14 200537994 and methyl acrylate glycidyl, copolymers include ethylene units, glycidyl methacrylate units and ethyl acrylate glycidyl units or copolymers include ethylene units, glycidyl methacrylate units and an acetic acid Ethylene unit. Particularly preferred copolymers used include ethylene units and glycidyl methacrylate units. In addition, the epoxy group containing the ethylene copolymer preferably has a melting index (MFR: JIS K7210, measurement conditions of 190 ° C and 2.16 kg) of 0.5 to 100 g / 10 min, more preferably 2 to 50 g / 10min. In this range, the resin substrate has good mechanical properties and is suitable for obtaining a liquid crystal polyester. The epoxy copolymer content in the metal-coated resin casting of the present invention ranges from 0.1 to 25% by weight, more preferably from 10 to 20% by weight based on 100% by weight of the liquid crystal polyester. When the content is less than 0.1% by weight, the adhesion between the resin substrate and the metal layer may decrease. On the other hand, when the content exceeds 25% by weight, the heat resistance of the resin substrate becomes worse, and the plasticity of the resin composition decreases. The metal material of the metal layer of the metal-coated resin casting of the present invention is not limited. For example, the metal material may be copper, nickel, gold, aluminum, titanium, molybdenum, chrome crane, tin, copper, brass, nickel road, and alloys thereof. If necessary, an inorganic filler may be added to the resin composition to strengthen the resin substrate. For example, in this example, a fiber-like inorganic filler is added to the resin composition. The fiber-like inorganic filler may be glass fiber and carbon fiber. It is preferable to add the fiber-like inorganic filler in a range of 5 to 500 weight percent. In this example, it is possible to increase the strength of the resin substrate without reducing the adhesion of the metal layer. In addition, it can effectively prevent cracks in the area of the resin-based bonding wire. In addition, the preferred fiber diameter range is 6 to 15 / z m, and its aspect ratio 15 200537994 ranges from 5 to 50. When the fiber straight passes less than

Disperse the inorganic filler or cast concrete in the resin; exactly, the resin synthesis is bad. In addition, the composite filler is easy to be damaged. On the other hand, when the fiber diameter is larger than 15 /, jW produces uneven dispersion. The uniform distribution makes the resin substrate mechanical = iron because of the unevenness of the inorganic filler and the lack of smoothness of the substrate. When using the metal of the present invention, each has its own. When the resin-based circuit board is caused, the lack of smoothness is caused at this time. 2 When the resin casting is used as the casting electric length-to-width ratio is less than 5, the reliability in the welding line area. On the other hand, when the length-to-width ratio is greater than 50 Sa, the fracture per work will increase. The organic filling capacity f is in contact. The plasticity of the blended two-collar fat-bonded silk was reduced when it was kneaded. Reducing resin-based linear expansion machine filler. In this case, the preferred thin "two" filaments are treated as two and the length is 1G to 50 m. The use of ^ 1 dimension diameter ⑺ to 5 / z m inch stability parts does not have 4 :; Γ / 可 彳 ㈣ has a good scale. Improved surface strength can effectively provide surface correction strength. During the process, the resin casting of the present invention is used as the electrical modification 'in this example. The detail can be carbon titanate, potassium titanate, potassium titanate, thief IP, zinc oxide, oxidized acid fibrillated sulfuric acid. In this example == Mom, magnesium carbonate, carbon., _ ^ ^ ,, ,,. J τ Using titanate or borate filaments, the effect of reducing the linear linear coefficient of the substrate is very high. In addition, winter salt can reduce the dielectric tangent loss of the resin substrate and can improve the adhesion of the metal layer. In addition, when the resin composition contains short fibers such as filaments as the inorganic filler, as compared with the use of long fibers as the inorganic filler, the orientation of the short fibers can be controlled at each day t when the resin composition is manufactured. Therefore, regarding the linear expansion coefficient and shrinkage of the line 16 200537994, the obtained substrate has uniformity. As a result, the deformation and deformation of the resin substrate can be non-uniform to a resin casting having high dimensional accuracy. This =, Yad

The second and second rhyme flatness, the good flatness will be affected by the temperature = the resin substrate has these advantages. The best range of the second and special metal layers is that the number of filaments is 20 to 235. Hundred and two ^ about 100 weight percent of liquid crystal polyester. Within this range, when a flip chip is bonded to a 1C wafer to a resin substrate, a bump-bond bond with high reliability will be formed. By kneading the mixture of liquid crystal polysaccharides, granules of Aguchi were prepared, and an extruder was used to obtain epoxy groups and filaments containing an ethylene copolymer. Feather ... In addition,-flat-shaped inorganic fillers such as talc, mica, glass flakes, ^ 7 and% moisturizer. From the viewpoint of providing good dimensional stability and a high degree of resin substrate, 'It is preferable that the flat-shaped inorganic filler has an average length of ί —, V m is more preferably 1 to 50 // m, and has a length-to-width ratio of 2 to 60 is more equal to 10 to 40. From preventing the non-uniformity of the resin substrate to improving the size% = property without causing a decrease in the adhesion of the metal layer, it is preferred to add the flat plate 2 heat resistance: the number of fillers ranges from 10 to 40 weight percent. 100 weight percent. The above-mentioned fibrous inorganic fillers, filaments, or plate-shaped inorganic fillers can be used as such. Two or more of them may be used in combination with each other. In addition, inorganic fillers such as filial blades or needle-shaped can also be added to the resin composition. ^ The metal-coated resin casting of the present invention can be obtained by casting a resin composition containing a liquid crystal polyester and an oxy group containing an ethylene copolymer. If the non-dragging material is needed, it can be stuck on the resin substrate and the resin substrate. A metal layer is formed on the surface. The procedure for preparing the resin substrate is not limited. The increase in effect will be described later. It is preferable to knead the liquid crystal polyester with the epoxy group of the ethylene-containing copolymer at a temperature higher than the temperature at which the liquid crystal polyacetate begins to flow. In addition, the temperature at which the preferred liquid crystal polyester starts to flow is 270 ° C or higher. For example, the resin substrate is formed by kneading a liquid crystal polyester mixture having an initial flow temperature of 320 ° C and an epoxy group containing an ethylene copolymer at a temperature of 340 ° C, and then using a biaxial The pellets are obtained by an extruder, and then the desired shape is obtained by injection molding. Comparing the granulated form with the granulated form, the adhesion of the metal film tends to increase with or without heat treatment. In the case where the resin substrate is formed by injection molding, the preferred resin composition has a melt viscosity ranging from 100 to 200 poises and a shear rate of 1000 / second. The temperature at which the flow begins is defined as when the die-casting material is extruded through a nozzle at a load of 100 kgf / cm2 (980 N / cm2) and a heating rate of 4 ° C / min, the internal diameter of the nozzle is 1 mm in length The temperature is 10mm, and the melting viscosity measured by a capillary rheometer is 48000 poise. The relevant standard is the Japanese Industrial Standard K6719-1977. For the formation of a metal layer, it is preferred that the substrate be heat-treated at a temperature lower than the temperature at which the liquid crystal polyester starts to flow. More preferably, there is a boundary between low temperature and high temperature. Low temperature is the temperature at which the liquid crystal polyester begins to flow minus 120 degrees; high temperature is the temperature at which the liquid crystal polyester starts to flow minus 20 degrees. In this case, it can further improve the adhesion of the metal layer and reduce the thermal expansion coefficient of the resin substrate. In addition, it can also reduce the dielectric tangent loss of the resin substrate. Therefore, the metal-coated resin casting of the present invention can be used as a foundry circuit board having excellent RF (radio frequency) properties. When the heat treatment temperature is lower than the low temperature boundary, the heat treatment effect is not significant. On the other hand, when the heat treatment temperature is higher than the high temperature boundary, warpage and deformation of the resin substrate may occur. The conditions for the preferred heat treatment 18 200537994 are in an inert gas such as nitrogen and have a residual oxygen concentration of less than 1%, more preferably less than 0.5%. In addition, from the viewpoint of preventing the essential change of the resin substrate, the preferred heat treatment time is in the range of 1 to 4 hours. Prior to the formation of the metal layer, a plasma treatment is preferably performed on the surface of the heat-treated resin substrate. The epoxy group containing the ethylene copolymer in the resin composition has highly reactive functional groups, and the surface of the resin substrate can be effectively activated by plasma treatment. Therefore, the effect of plasma treatment will greatly increase the adhesion of the metal layer. Plasma treatment can be performed using conventional plasma processing equipment. For example, a plasma processing apparatus includes a pair of electrodes which are arranged face to face in a reaction chamber and a radio frequency unit for applying a radio frequency electric field is used in the middle of the electrodes. In this case, a resin substrate was placed on one of the electrodes, and the reaction chamber was decompressed to about 1 to 4 Pa. Then, a plasma-forming gas such as ammonia and nitrogen was formed in the reaction chamber so that the internal pressure became in the range of 8 to 15 Pa. Next, 300 watts of RF power is applied between the electrodes during 10 to 100 seconds. The RF unit is used to generate the plasma, and then the cations and free radicals in the plasma are generated to obtain the activation of the surface of the resin substrate. The nitrogen polar group or the oxygen polar group has the ability to easily bond with metal, and during the plasma treatment, the cation collision is given to the surface of the resin substrate, and the adhesion of the metal film can be further improved. The state can be freely determined in conception, so that the surface of the resin substrate will not be excessively rough by plasma treatment. In addition, the type of gas formed by plasma will not be limited. For example, nitrogen is preferably used as electricity as described above. The gas formed by the slurry. In this case, a nitrogen plasma is used, which can reduce the desorption of carbon dioxide gas because the ester bond of the resin substrate is destroyed, and Compared with the use of oxygen plasma. As a result, it can avoid reducing the intensity of the surface portion of the resin substrate. 19 200537994 Deposition and ions: Vapor deposition such as sputtering, formation of a vacuum film is continuously completed. In the present case, the DC splash dream reaction chamber was used to decompress the reaction chamber to ^ 1 (^ with the approximate substrate in it and into the reaction chamber, so that Internal pressure = Pa and then the inert gas argon volts of DC was used for bombardment ^ again to about 0.1 Pa. Next 500 copper films were formed on the resin substrate. The thickness of the metal was 2_ legs and its internal product For example, a resin substrate with a milliampere of electrons flowing in the sintered medium to 800 masses. Therefore, the thickness of the metal material is about 300, so that the metal material is steamed. The copper film of ilm is formed In the resin-based bank chamber, the rotor is “for example, the vacuum of the reverse case in which the substrate is turned inside. In addition, the radio frequency power of the metal material being evaporated is used; in the dry enclosure. Then 500 watts and resin in the case” Requires offset for electrode 2⑽ to be in the reaction chamber A plasma is formed. As a result, a metallic copper film having a thickness of 0 nm is formed on the resin substrate. The present invention particularly relates to a genre Gan # 丄 士 resin substrate which can achieve high adhesion, and will be treated with electricity. Using the steaming method of the present invention, such as', and the binadium = physical vapor deposition method during the physical vapor deposition method, in other words, in the physical vapor deposition / 1 hunter implanted Nanzhao metal particles into the surface portion of the resin substrate 20 200537994 effect, and a chemical modification effect brought about by plasma treatment, in addition to the orbital treatment effect, which can obtain a strong chemical bond at the interface between the resin substrate and the metal layer, without the need for a occupant and Chemicals. In addition, when the mechanical strength and hardness degradation of the surface portion of the resin substrate occur, however, in the present invention, the liquid crystal polyacetate can react with the two-reading groups, and the surface portion of the resin substrate is resistant to tearing. The crackability is obvious. It can prevent the surface part of the resin substrate from being as strong as possible. It has a metal sheet with a thickness of tens of micrometers to hundreds of micrometers. Anri: = ,, 1 on the resin substrate. Here is an example. The metal layer is formed in the circuit diagram: prolong or improve the adhesion effect between the two becomes smaller day old moment τ, because the resin substrate is not sufficient to have a chemical effect. Lu Tuo Gen Bingjia is based on the viewpoint that the metal coating parts of the present invention can be used as a casting electrode. In addition to the circuit part, it can effectively remove unnecessary metal layers and reduce the adhesion of the metal layers. It can be recommended to use the laser pattern before it is formed. It does not need to be processed in the film shape θ in order to improve the riding force of the metal layer. It can form a good and accurate circuit diagram. The laser pattern is formed without reducing the circuit. Accuracy, this is due to the fact that Jin Ke uses the rough surface of the substrate. Therefore, the resin rotating part of the present invention is also suitable for MID. After the Niu Liΐ pattern is formed, an additional metal reed shape can be added by the electrolytic clock: Two = on the circuit pattern so that the entire thickness becomes 5 =: After the completion, if necessary, the ship can be thick and thick. To the residue of the metal layer. In addition, it has several micrometers. An E layer can be formed on an additional metal layer to make a circuit. Use the resin scale of the present invention to obtain a circuit pattern with a pattern in it. 21 200537994 Example Explain the invention (synthetic sr of liquid crystal polyester) according to a preferred example.舲 9 丨 1 gram (6.6 Moore) of p-Aminobenzoic acid, 409 grams (2.2 Moore) of H '/ dihydroxydiphenyl, 274 grams (1.65 Moore) of p-benzenediphenyl Acetic acid, 91 g (0.55 moore), m-benzyl-acetic acid, [235 g (12] moore) acetic anhydride and gram methyl m Device, torque meter, gas inlet pipe, thermometer and reflux condenser. • The gas in the frontal reactor is replaced by gas. The temperature of the synthesized mixture was then raised to 150 ° C over 15 minutes under nitrogen flow and refluxed at 150 ° C for three hours. Thereafter, 1.69 g of 1-fluorenimidazole was further added to the mixture, and the resulting compound was heated to 17Q minutes to heat the mixture from i5 (rc to 32 ° C. At this time, the by-product of acetic acid and unreacted The acetic anhydride is evaporated and removed. When the torsional force begins to increase, it is regarded as the end reaction, and the synthesis product is removed in the reactor. The solid content of the synthesis product is cooled at room temperature and the crude product Can be crushed. The powder obtained is heated by passing 1 / J under nitrogen. The main dish is heated to 250 C. In addition, the powder is reheated from 250 ° to 288 ° C for 5 hours. It was kept at 288. (: It lasted for 3 hours to promote the solid phase polymerization reaction. Therefore, the liquid crystal polyester was obtained. The measurement of the starting flow temperature of the liquid crystal polyester was obtained at 320 ° C by a flow tester. (CFT-5 was manufactured by Shanru Yigu Corporation). (Synthesis of Liquid Crystal Poly S2) 911 grams (6.6 moles) of p-hydroxybenzoic acid, 4.09 grams (22 moles) 4,4'-dihydroxydiphenyl, 274 g (65 Moore) terephthalic acid,% g (0555 Moore) Isophthalic acid, 1235 g (121 moles) of acetic anhydride were placed in a reactor, which had a stirrer, a torque meter, a nitrogen introduction tube, a thermometer, and a 22 200537994 flow condenser. The gas in the reactor was then charged with Nitrogen was used to replace it. Then the temperature of the synthesized mixture was raised to nc over 15 minutes under dynamic conditions and refluxed at 150 C for three hours. The resulting mixture was heated over 15 minutes to heat the mixture from 15 (rc to 3 = C. At this time, the by-products of acetic acid and unreacted acetic anhydride will be evaporated and the mouth will be removed. When the torque starts to increase, it will be regarded as the end reaction, and the synthesized product will be removed during the reaction. The solid content of the synthesized product was cooled and crushed by a coarse ground stick. The resulting powder was heated by # from room temperature to 250 ° C under nitrogen for 1 hour. In addition, the powder was reheated from 250 ° C to 278t. After 5 hours, it was kept at 278 ° C for 3 hours to promote the solid phase poly-a reaction. Therefore, the liquid crystal polyester S2 was obtained. The starting flow temperature of the liquid crystal polyester was measured at 32CTC. By flow It is obtained by the tester. On the other hand, the epoxy group containing the ethylene copolymer has a first bond of Bf_e, BF-2C, BF-7, and BF-2B (made by SUMITOMO CHEMICAL). The first bond BF-E is an ethylene-fluorenyl acrylic glycid scale copolymer ^ (fluorenyl-acrylic acid glycidyl ether content 12% by weight, g / 10 φ min). The first bond BF-2C is an ethylene -Glycidyl methacrylate copolymer (glycidyl methacrylate content, 6 weight percent, g / 10 minutes). The first bond BF-71V [is a copolymer of ethylene-glycidyl ether methyl acrylate (glycidyl methacrylate content 6% by weight, acrylate acrylate content 30% by weight, g / iq minutes). The first bond BF-2B is an ethylene-methacrylic acid glycidyl ether-vinyl acetate copolymer (glycidyl methacrylate content 12% by weight, vinyl acetate content 5% by weight, MFR = 3 g / 1 〇 minutes). The value of MFR (Melting Flow Rate) is measured at a temperature of 190 ° C at a load of 2160 grams, and is based on JISK7210 (Japanese Industrial Standard). 23 200537994 If necessary, an inorganic filler, a milled glass fiber (MGF: EFH-7501 is manufactured by CENTRAL GLASS, fiber straight 10 / zm, length to width ratio 10), aluminum borate filament "alb 〇R £ x ys3a ”(manufactured by Shikoku Corp ·, fiber diameter: 0.5 to ι · 〇, length · 10 to 30_), and / or one talc ,, χ-50 ,, (Congnufactured by NIPPON TALC CO ·, LTD ·, average length: 20 to 25 // m, aspect ratio: 5 to 10) can be used. (Example 1) 100 weight percent of liquid crystal polyester S1 and 5 weight percent of epoxy group containing ethylene copolymer, 'BF-E' and 07 weight percent of milled glass fiber (MGF) ', EFH-7501 "is mixed as an inorganic filler to obtain a resin composition. The pellets of the resin composition were then prepared at 340. 〇 Obtained by using a worm-shaped machine (PCJvi-30 manufactured by Ikegai Tekko). The pellets of the resin composition were injection-molded at a cylindrical temperature of 35 (rc and a mold temperature of 13.0 ° C) using an injection molding machine (PS40E5ASE manufactured by Nissei Plastic Industrial) to obtain a resin substrate having a size of 4〇mm> (30mm x 1mm. Then, the surface of the resin substrate is plasma treated. After the plasma treatment, the metal film is formed on the plasma treated by a DC (direct current) magnetron sputtering device. On the surface of the lipid substrate. That is, the resin substrate is first placed in the reaction chamber of the plasma processing apparatus, and then evacuated to about 10_4 Pa. In addition, nitrogen is introduced into the reaction chamber so that the The pressure was changed to 10 Pa, and then the resin substrate was subjected to electrical treatment for 30 seconds, in which 300 watts of RF power was applied between the two poles of the plasma treatment device. After the plasma treatment, the reaction chamber was evacuated to Less than ΚΓ4 Pa, and then argon gas was introduced into the reaction chamber to make the pressure to 0.1 Pa. After applying 500 volt 24 200537994 to hit the metal copper wire, the thickness of the metal film was so light that The pattern for 51_ was formed on metal reeds to obtain two; (Examples 2 to 5) The thickness of the soil peel strength test was 15_. Test ^ Off off strength Zhao Dan Qijin I The method is generally the same as Example 1, except that it is used武 门; 6 合物 合 ΒΜ epoxy thin film, which is shown in Table 1 °. Method and use, peeling strong, Nadi's manufacturing method is 10%, 100%, 15%, 100% reset, liquid crystal polymer Ester "S2, mixed with one hundred and eighty's of a hundred knives than epoxy containing ethylene copolymer, BF_E, and 67% of glass fiber (MGF), and" Ca 75〇Γ "to obtain resin (Example 7) Uniquely, there is a mounting epoxy of a resin substrate having a circuit pattern for peel strength test, BF-2C, instead of, BF-E ,. (Example 8)-One with circuit diagram The resin cube used for the peel strength test is made in the same shape, except that it uses 15% by weight of laminating oxygen containing ethylene copolymer, BF-7M, instead, BF_E ,. C Example 9) — The manufacturing method of a resin substrate with a circuit pattern for peel strength test 25 200537994 is almost the same as in Example 1, except that 15% by weight of epoxy group containing ethyl compound, BF-2B, instead of, BF-E ,, ◦, ', water (relative example 1) A resin with a circuit pattern for peel strength test The manufacturing method of the substrate is generally the same as that of Example 1, except that the ethylene copolymer containing dioxyl is not used. About each of Examples 1 to 9 and 90 degrees of the circuit pattern with respect to Example 1

Peel strength was measured by measuring the peel strength using a universal testing machine (EG Ding was manufactured by SMmadzu Corpomt Wei). In addition, according to astj ^ D648 under the load U2Mpa, the deflection temperature (dtul) under the forward load is shown in Table 10, and the results in Table 1 show that the adhesion of the circuit pattern in the example 1 form is greater than the circuit pattern of the phase y towel Among them, the relative example 1 did not use ▲ Youcai / Xiaya using liquid crystal polyester magic "synthesis can further improve the adhesion. = ^ Zai 3, 7 and 9 flexure temperature under the resin substrate) The epoxy group of the polymer polymer is used, and the ethylene copolymer is at -r fuldi ', 2% of the acetone of 8G weight I, which is higher than the tree ^ polymerization of Example 8; sub = Greek copolymer Age, compared with the long-term containing molecular towels such as Wuli Baidao than the ene unit of this olefin unit. 200537994 Table 1

Examples Comparative Example ^ 口 --- 1 2 ό 4 5 6 7 8 9 1 Lost crystals, esters (weight percentage) t S1 S1 S1 S1 SI S2 SI SI SI SI '" ---- 100 100 100 100 100 100 100 100 100 100 Containing ethylene copolymerization BF-E BF-E BF-E BF-E BF-E BF-E BF-2C BF-7M BF-2B None Epoxy group (weight percentage) 5 10 15 20 25 10 15 15 15 Inorganic filler (VtGF) (% by weight) 67 67 67 67 67 67 67 67 ----- 67 67 Peel strength 036 0.42 0.40 0.39 0.43 0.36 0.41 One ----- 0.40 0.38 0.29 Under load Deflection temperature ---- 266.0 259.6 255.4 243.9 232.0 258.0 266.0 232.0 255.4 279.0 The results show that the adhesion of the circuit patterns in Examples 1 to 9 is greater than the circuit pattern in phase firing = 1, where the phase No epoxy group was used in the compound. In addition, in Comparative Examples 2 and 6, it can be seen that the deflection temperature (DTUL) under the load of the resin substrate of each towel is used, and the epoxy group of the fraction is used. The ethylene copolymer has a weight of greater than 80. Percentage of ethylene units, which is higher than that of the tree 27 of Example 8 200537994. The olefinic copolymer containing the ethylene copolymer in Example 8 has less than 80 weight units of soil in one molecule. From the viewpoint of heat resistance, it is preferable to use an ethylene unit containing 100%. Cyclooxyl groups of ethylene copolymers of ethylene units with a weight percentage of greater than 80 weights (Examples 10 to 13) In Examples 10 to 13, a system of right emperor θ, is produced by ^ 七 + * / A Production method and example of Shuyueyue substrate with circuit pattern for peel strength test} Da_tong, epoxy group of copolymer, 'BF_E' is ⑺weight / with ethylene for heat treatment, the conditions show In Table 2, the second treatment of the electric poly knife and the resin substrate (relative example 2)-one with a circuit diagram _ 关 _ 赖 ΐ is generally the same as in Example 1, except that the heat treatment and the bottom of the wire containing B are not used, and the conditions _ As shown in Table 2, the electrical ^ curve ^^^ and the circuit _ ㈣ degree peeling _ degree and the measurement of the DTUL under load are the same as the above example! In the relative example 8, the right two dielectric tangents of the mouth Loss of ㈤㈠. In addition, 阙 鲜 2 will be the resin base ^ month 1 mouth t bottom of the heat-resistant hot cake is estimated according to the following method. That is θ2,-, water 卩 〇 / Fork into the welding bath for 60 seconds, and Check that deformation occurs. One of the best: ◊ deformation is measured. However, the impedance _ degree is measured at 1 for Examples 2, 10 to 13. Gigahertz In Relative Example 2, the SHUNA / Material Analyzer 'HP4291A. Measurements, the results are shown in ΪΓ (D dish) and the heat resistance temperature is not changed. 28 200537994

Table 2

It can be known from 1Q to 13 that the heat resistance of the circuit pattern spot resistance has been further improved by the heat treatment circuit pattern. In addition, from the relative example BU2 ^ (_) When the Tianqi and Yuyue substrates containing ethylene mound polymers have% gas bases including the material, the dielectric tangent is lost by heat treatment 29 200537994 (tan δ) will rise. (Example 14) Method _32, The manufacturing method of the resin substrate used for the peel strength test is 10 dwt. 100% of the same as' except 100% by weight of liquid crystal polyester, S2, and mixed ^ Epoxy group of polymer, BF_E ,,, 30 heavy μ knife ,,, read broken glass fiber (MGF), coffee, 5Q weight baishi, xso ,, L,; e, SjA and 20% by weight of talc X〇0 to obtain the resin composition. (Examples 15 to 21) Examined ==== There are circuit patterns for peel strength test length and width example \ F), the glass fibers (MGF) have different diameters Proportion to long-term, is shown in Table 3. Guan ^^ system, resin-based welding line strong button, quilt. In the first figure, the number, 2 "represents the needle point washing mouth M ·· 3 number ^ Extensive welding lines. After the heat treatment is completed, the test sample is under nitrogen during the chat, and the weld line inspection is based on the following solution. 〇: No crack occurred X ··· Crack occurred after heat treatment In addition, the 90-degree peel strength of the circuit pattern after heat treatment is described in Example 1, and the results are shown in Table 3. As can be seen from Table 3, examples Η to 2;! 'S circuit diagrams are good. In addition, Comparative Examples 14 to 18 and Examples 19 to 2 show more fibrous inorganic fillers, which have a diameter of 6 to 15 Second, f ΜΠ1 and Chang Jian 30 200537994 ratio of 5 to 50 to get good welding strength Table 3

19 20 21 S1 S1 S1 100 100 100 BF-E BF-E BF-E 10 10 10 30 30 30 φ ΙΟμπι φ 1 Ομηι φ20μηι 3 100 10 50 50 50 ^ 20_ 20 20 0.33 0,43 0.33 2 < XX (Example 22 to 26) In each of Examples 22 to 26, a manufacturing substrate and an example of a resin substrate having a lightning test are shown in the figure. The liquid crystal polymer is expressed as a percentage of peel strength. "Item = In addition to the weight of epoxy groups, BF-E "and quantity_ one has ethylene copolymer YS3A" to obtain cis-lipid silk. When it is in the heart, it wakes up 31 200537994 C Examples 27 to 31) 27: One of U1 has a circuit pattern for peeling The manufacturing method and example of the resin substrate of the strength office are roughly the same, except that the percentage of liquid crystal poly vinegar "sr, mixed with 10% by weight containing ethyl chloride f characters Table 4 ^ Exciting filament" Table 4 shows talc, X_50 "to obtain a resin composition. In Example 22_H of Xinguanfang 1, after the heat treatment, the resin substrate was held at 250 ° C for 1 hour under nitrogen, and the 90-degree peel strength of the circuit pattern was measured as described in Example 亍 1. In addition, the linear expansion coefficient of the resin substrate is measured according to the following method. That is, 'delete a test piece from the central part of an injection fin'. The size of the injection scale is 80mmx80mmx3mm. The size of the resin flow orientation of this test piece is plus m, and the size from the rectangular orientation to the resin flow orientation is i_〇. mm. Then, the linear expansion coefficient of the test piece was measured by TMA, and the results are shown in Table 4. '' From Examples 22 to 26 'When maintaining good adhesion of the circuit pattern and from the viewpoint of reduction = line = expansion coefficient, it is preferable to add the number of filaments in the range of 20 to -200 dollars. 100% by weight of liquid crystal polymer. Regarding the examples 27 to 31, _stone is made. When the amount of talc is increased, the linear miscellaneous coefficient between the resin flow orientation and the rectangular orientation decreases. By adding talc, the isotropic linear expansion coefficient will decrease. However, from a balance method that can be achieved, the coefficient of linear expansion and good circuit adhesion are preferably added by adding talc to 10 to 40 weight percent, about 100 weight percent of liquid crystal polyacetate. Table 4 32 200537994

Examples 22 23 24 25 26 27 28 29 30 31 Liquid day to day 8 SI SI (% by weight) S1 S1 S1 S1 S1 S1 S1 S1 SI 100 100 100 100 100 100 100 100 100 100 100 Containing ethylene total BF-E BF-E BF-E BF-E BF-E BF-E BF-E BF-E BF-E BF-E Polymer ring gas group (weight percentage) --- ~~~ __ 10 10 10 10 10 10 10 10 10 10 10 Inorganic filler (filament) (weight percentage) 20 67 100 235 290 90 80 70 60 50 Inorganic filler 0 0 0 0 0 10 20 30 40 50 (slip; 5,) (weight percentage) — ~~ .__ Peel strength 0.45 0.43 0.43 0.33 0.30 0.45 0.44 0.38 0.33 0.30 Coefficient of linear expansion (MD / TI3) X l (T3 / 〇C 19/28 13/18 9/14 7/12 5/10 10/13 12/14 13/16 15 / 18 18/18 --------- L ---- Applicability of industry As shown in the above example, the present invention provides an excellent adhesion 33 200537994 Upper Ai Yayan is a coated resin rotor. In addition, The resin substrate is heat-treated, and it can be :: It is a cloth-made resin casting, which can improve the adhesion and reduce the dielectric. These advantages will be better, but the electronics industry, especially the technical field that requires high-frequency characteristics. Detailed description ^ L is only the best of the present invention-specific embodiments to limit the features of the present invention are not Restricted to this, not all the scope of the present invention shall be used as the following. Please refer to the patent scope ^, the spirit of the patent scope of the present invention and similar changes 蓺 I, examples, should be included in the scope of the present invention Any changes or modifications that are familiar with this technology in the field of the present invention can be easily considered in the patent scope of the following case. [Simplified illustration of the drawing] Brother-picture is an estimate of the strength of the sample and weld line. [Illustration of Symbols of Main Components] 益 ^ > w 34

Claims (1)

200537994 10. Scope of patent application: 1. A metal-coated resin casting, including: A metal-coated resin casting includes a substrate made of a resin composition and a metal layer formed on the substrate, wherein the resin composition includes 1 至 30 重量 ％ 的 A liquid crystal polyester and an epoxy group containing an ethylene copolymer, the molecule containing the epoxy group of the ethylene copolymer contains a 50 to 99.9 weight percent ethylene unit with at least one 0.1 to 30 weight percent of Unsaturated acid-glycidyl vinegar units and one unsaturated glycidyl ether unit; and ®-the epoxy group content of the ethylene-containing copolymer is in the range of 0.1 to 25 • weight percent, about 100 weight percent of the liquid crystal polymer ester. 2. If applying for a special application; each of the metal coating resins described in item 1 of the fij range, where the reaction product liquid crystal polyester is obtained by transesterifying at least one aromatic dicarboxylic acid with an aromatic hydroxycarboxylic acid The reaction with polycondensation and the preparation of a fluorinated compound is by hydration of at least one aromatic diol and one phenolic hydroxyl group of an aromatic hydroxycarboxylic acid having a fatty acid anhydride. 3. The metal-coated resin casting described in item 1 of the scope of the patent application, wherein the transesterification and polycondensation reaction are performed in the presence of an imidazole compound, which is represented by the following chemical formula: Wherein in the chemical formula, R1 to R4 represent: a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a cyano group, a carbon number 35 200537994, a cyanoalkyl group having a head number of 1 to 4, Carbon radicals, amino groups, amino groups, carbon atoms, and cyano-oxygen groups have a carbon number of 1 to 4, and air-to-fired groups of 4 to 4, with filaments and fibers. ―Benyl, benzyl, phenylpropyl 4 1 Pins of metal, and the epoxy group of the two-hole ... To 95% by weight :: Early wood with 5 to 15 weight I percent 屮 5 small soil ... The knife ratio of ethylene yuan and unsaturated glycidol and slow acid glycidyl vinegar list 5, ς 申 ㈣ 丨 rhyme metal_ Compilation =: Finished articles § have similar fibrous inorganic fillers, _ machine_ has a metal coated tree transfer piece with a diameter of 6 to 15㈣ and a length to width ratio of 5 to 50 plus 6 jobs in the first job, Lizhong Today's weight percent of liquid crystal polyacetate. As for the metal described in item 1 of the 7th application series, the fat composition contains 10 to 40% by weight of a flat plate, and its ^ is related to the percentage of liquid crystal polyacetate by weight. The materials of the metal coating described in item 1 of Shenqiao's patent scope are copper, nickel, gold, of which the copper copper, nickel chromium and its alloys. Tin | mouth, 9, = Please apply for the metal-coated resin described in item 1 of the patent scope, 1 is formed in a circuit pattern from the metal layer to the metal layer. ', ^ 10 A method for manufacturing a metal-coated resin casting, comprising: scaling a resin composition to obtain a substrate; and forming a metal film on the surface of the substrate; 36 200537994 wherein the resin composition includes a liquid crystal polyacetate and An epoxy group containing an ethylene copolymer. The molecule containing the epoxy group of the ethylene copolymer contains one 50 to 99.9 weight percent ethylene unit and at least one 0.1 to 30 weight percent unsaturated glycidyl glycidyl ester unit and one unsaturated glycidyl ether unit. 1 至 2 5 重量 ％。 About 100% by weight of the liquid crystal polyester, the epoxy group-containing ethylene copolymer content range is from 0.1 to 2 5 weight percent. 11. The method for manufacturing a metal-coated resin casting as described in item 10 of the scope of the patent application, further comprising a step of plasma-treating the surface of the substrate. 12. The method for manufacturing a metal-coated resin casting as described in item 10 of the scope of the patent application, wherein the metal layer is formed by physical vapor deposition. 13. The method for manufacturing a metal-coated resin casting according to item 10 of the scope of patent application, further comprising a step of plasma-treating the substrate, the heat treatment temperature being between a low temperature and a high temperature boundary, the low temperature boundary is The temperature at which the liquid crystal polyacetate starts to move is minus 120 degrees. 5 The south temperature boundary is the temperature at which the liquid crystal polyester starts to flow minus 20 degrees. 14. The method for manufacturing a metal-coated resin casting according to item 10 of the scope of the patent application, wherein the liquid crystal polyester is prepared by transesterification and polycondensation reaction of at least one aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid. And a halogenated compound is prepared by halogenating at least one aromatic diol and a phenolic hydroxyl group of an aromatic hydroxycarboxylic acid having a fatty acid anhydride. 15. The method for manufacturing a metal-coated resin casting according to item 14 of the scope of the patent application, wherein the transesterification and polycondensation reaction are performed in the presence of a miso compound, which is represented by the following chemical formula: 37 200537994 Ri The atomic formula can be represented by: hydrogen atom, silk with carbon atoms Γ to ^ 1, warpyl group, cyano group, with a number of carbon atoms: & cyanofluorene group, with 1 to 4 carbon atoms The cyanoalkoxy group n I has 4 ammonium groups having 1 to 4 atoms, amine groups having 1 to 4 amino groups, phenyl, benzyl, phenylpropyl, and formamyl . Manufacture of metal __ received in item 1G Made in this gold step is to shape the circuit pattern by laser pattern forming 38